This invention concerns novel liquid crystal polymers (LCP) materials, novel intermediates, methods for preparing them and their use in devices.
Liquid crystals can exist in various phases. In essence there are three different classes of liquid crystalline material, each possessing a characteristic molecular arrangement. These classes are nematic, chiral nematic (cholesteric) and smectic. A wide range of smectic phases exists, for example smectic A and smectic C. Some liquid crystal materials possess a number of liquid crystal phases on varying the temperature, others have just one phase. For example, a liquid crystal material may show the following phases on being cooled from the isotropic phase:-isotropic-nematic-smectic A-smectic C-solid.
Materials possessing a smectic A (SA) phase may exhibit an electroclinic effect. The electroclinic effect was first described by S Garoff and R Meyer, Phys. Rev. Lett., 38, 848 (1977). An electroclinic device has also been described in UK patent application GB-2 244 566 A. This particular device helps to overcome the poor alignment problems of electroclinic (EC) devices using a surface alignment that gives a surface tilt within a small range of angles.
When a smectic A phase is composed of chiral molecules, it may exhibit an electroclinic effect, i.e. a direct coupling of molecular tilt to applied field. The origin of the electroclinic effect in a smectic A phase composed of chiral polar molecules has been described by Garoff and Meyer as follows. The application of an electric field parallel to thesmectic layers of such a smectic A phase biases the free rotation of the transverse molecular dipoles and therefore produces a non-zero average of the transverse component of the molecular polarisation. When such a dipole moment is present and coupled to the molecularchirality, a tilt of the long molecular axis (the director) is induced in a plane perpendicular to the dipole moment.
In thin samples, for example 1-3 mm, and with the smectic layers tilted or perpendicular with respect to the glass plates the electroclinic effect is detectable at low applied fields.
In an aligned smectic A sample a tilt of the director is directly related to a tilt of the optic axis. The electroclinic effect results in a linear electro-optic response. The electro-optic effect can manifest itself as a modulation of the effective birefringence of the device.
Electroclinic (EC) devices are useful, for example, in spatial light modulators having an output that varies linearly with applied voltage. A further advantage of EC devices is that they have high speed response times, much faster than twisted nematic type devices. One known type of ferroelectric device is bistable, in contrast the EC device is not bistable and has an output that varies linearly with applied voltage.
The electroclinic effect is sometimes referred to as the soft-mode effect see GAndersson et al in Appl. Phys. Lett., 51, 9, (1987).
In general terms, regarding the electroclinic effect, it is advantageous if on applying a small voltage there results a large induced tilt. An increase in induced tilt may result in an increase in contrast ratio. It is also advantageous if a large induced tilt can be obtained at as low a voltage as possible.
It is also advantageous if the relationship between molecular induced tilt and applied voltage is temperature independent. When an increase in applied voltage results in little or no change in induced tilt then the material being tested is generally referred to as exhibiting a saturation voltage effect.
By SA* is meant a SA phase which contains some proportion of chiral molecules.
Cholesteric or chiral nematic liquid crystals possess a twisted helical structure which is capable of responding to a temperature change through a change in the helical pitch length. Therefore as the temperature is changed, then the wavelength of the light reflected from the planar cholesteric structure will change and if the reflected light covers the visible range then distinct changes in colour occur as the temperature varies. This means that there are many possible applications including the areas of thermography and thermooptics.
The cholesteric mesophase differs from the nematic phase in that in the cholesteric phase the director is not constant in space but undergoes a helical distortion. The pitch length for the helix is a measure of the distance for the director to turn through 360xc2x0.
By definition, a cholesteric material is chiral material. Cholesteric materials may also be used in electro-optical displays as dopants, for example in twisted nematic displays where they may be used to remove reverse twist defects. They may also be used incholesteric to nematic dyed phase change displays where they may be used to enhance contrast by preventing wave-guiding.
Thermochromic applications of cholesteric liquid crystal materials usually use thin film preparations of the materials which are then viewed against a black background. These temperature sensing devices may be placed into a number of applications involving thermometry, medical thermography, non-destructive testing, radiation sensing and for decorative purposes. Examples of these may be found in D G McDonnell in Thermotropic Liquid Crystals, Critical Reports on Applied Chemistry, Vol. 22, edited by G W Gray, 1987 pp 120-44; this reference also contains a general description of thermochromic cholesteric liquid crystals.
Generally, commercial thermochromic applications require the formulation of mixtures which possess low melting points, short pitch lengths and smectic transitions just below the required temperature-sensing region. Preferably the mixture or material should retain a low melting point and high smecticxe2x80x94cholesteric transition temperatures.
In general, thermochromic liquid crystal devices have a thin film of cholesterogen sandwiched between a transparent supporting substrate and a black absorbing layer. One of the fabrication methods involves producing an xe2x80x98inkxe2x80x99 with the liquid crystal by encapsulating it in a polymer and using printing technologies to apply it to the supporting substrate. Methods of manufacturing the inks include gelatin microencapsulation, U.S. Pat. No. 3,585,318 and polymer dispersion, U.S. Pat. Nos. 1,161,039 and 3,872,050. One of the ways for preparing well-aligned thin-film structures of cholesteric liquid crystals involves laminating the liquid crystal between two embossed plastic sheets. This technique is described in UK patent 2,143,323.
Ferroelectric smectic liquid crystal materials, which can be produced by mixing anachiral host and a chiral dopant, use the ferroelectric properties of the tiltedchiral smectic C, F, G, H, I, J and K phases. The chiral smectic C phase is denoted SC* with the asterisk denoting chirality. The SC phase is generally considered to be the most useful as it is the least viscous. Ferroelectric smectic liquid crystal materials should ideally possess the following characteristics: low viscosity, controllable spontaneous polarisation (Ps) and an SC phase that persists over a broad temperature range which should include ambient temperature and exhibits chemical and photochemical stability. Materials which possess these characteristics offer the prospect of very fast switching liquid crystal containing devices. Some applications of ferroelectric liquid crystals are described by J S Patel and J W Goodby in Opt. Eng., 1987, 26, 273.
In ferroelectric liquid crystal devices the molecules switch between different alignment directions depending on the polarity of an applied electric field. These devices can be arranged to exhibit bistability where the molecules tend to remain in one of two states until switched to the other switched state. Such devices are termed surface stabilised ferroelectric devices, e.g. as described in U.S. Pat. No. 5,061,047 and U.S. Pat. No. 4,367,924 and U.S. Pat. Nos. 4,563,059. This bistability allows the multiplex addressing of quite large and complex devices.
One common multiplex display has display elements, i.e. pixels, arranged in an X, Y matrix format for the display of for example alpha numeric characters. The matrix format is provided by forming the electrodes on one slide as a series of column electrodes, and the electrodes on the other slide as a series of row electrodes. The intersections between each column and row form addressable elements or pixels. Other matrix layouts are known, e.g. seven bar numeric displays.
There are many different multiplex addressing schemes. A common feature involves the application of a voltage, called a strobe voltage to each row or line in sequence. Coincidentally with the strobe applied at each row, appropriate voltages, called data voltages, are applied to all column electrodes. The differences between the different schemes lies in the shape of the strobe and data voltage waveforms.
Other addressing schemes are described in GB-Z146, 473-A; GB-2,173,336-A; GB-2,173, 337-A; GB-2, 173629-A; WO 89/05025; Harada et al 1985 S.I.D. Paper 8.4 pp 131-134; Lagerwall et al 1985 I.D.R.C. pp 213-221 and P Maltese et al inProc 1988 I.D.R.C. pp 90-101 Fast Addressing for Ferroelectric LC Display Panels.
The material may be switched between its two states by two strobe pulses of opposite sign, in conjunction with a data waveform. Alternatively, a blanking pulse may be used to switch the material into one of its states. Periodically the sign of the blanking and the strobe pulses may be alternated to maintain a netd.c. value.
These blanking pulses are normally greater in amplitude and length of application than the strobe pulses so that the material switches irrespective of which of the two data waveforms is applied to any one intersection. Blanking pulses may be applied on a line by line basis ahead of the strobe, or the whole display may be blanked at one time, or a group of lines may be simultaneously blanked.
It is well known in the field of ferroelectric liquid crystal device technology that in order to achieve the highest performance from devices, it is important to use mixtures of compounds which give materials possessing the most suitable ferroelectricsmectic characteristics for particular types of devices.
Devices can be assessed for speed by consideration of the response time vs pulse voltage curve. This relationship may show a minimum in the switching time tmin) at a particular applied voltage (Vmin). At voltages higher or lower than Vmin the switching time is longer than tmin. It is well understood that devices having such a minimum in their response timevs voltage curve can be multiplex driven at high duty ratio with higher contrast than other ferroelectric liquid crystal devices. It is preferred that the said minimum in the response time vs voltage curve should occur at low applied voltage and at short pulse length respectively to allow the device to be driven using a low voltage source and fast frame address refresh rate.
Typical known materials (where materials are a mixture of compounds having suitable liquid crystal characteristics) which do not allow such a minimum when included in a ferroelectric device include the commercially available materials known as SCE13 and ZLI-3654 (both supplied by Merck UK Ltd, Poole, Dorset). A device which does show such a minimum may be constructed according to PCT GB 88/01004 and utilising materials such as e.g. commercially available SCE8 (Merck UK Ltd). Other examples of prior art materials are exemplified by PCT/GB 86/00040, PCT GB 87/00441 and UK 2232416B.
The unit that is the basic building block of a polymer is called a monomer.
The polymerisation process i.e. the formation of a polymer from its constituent monomers does not usually create polymers of uniform molecular weight, rather what is createdis a distribution of molecular weights. In order to describe a sample of polymer it is necessary to state the average number of monomers in a polymer this is called the degree of polymerisation (D.P). By how much the majority of polymer molecules differ from this average value (or to describe the spread of molecular weight) is called the polydispersity.
A number of different average molecular weights can be drawn from gel permeation chromatography (GPC) for a given sample including Mnxe2x80x94number average molecular weight and Mwxe2x80x94weight average molecular weight. The value used to calculate D.P. is usually Mn and polydispersity is usually defined as Mw/Mn.
Polymers can be made from different types of monomers, in which case the polymer is called a co-polymer. If two types of monomer join in a random fashion then the polymer is called a random co-polymer. If the two monomers form short sequences of one type first which then combine to form the final polymer then a block copolymer results. If short sequences of one of the monomers attach themselves as side chains to long sequences consisting of the other type of monomer then the polymer is referred to as a graft copolymer.
In liquid crystal (LC) polymers the monomers can be attached together in essentially two ways. The liquid crystal part or mesogenic unit of the polymer may be part of the polymer backbone resulting in a main chain LC polymer. Alternatively, the mesogenic unit may be attached to the polymer backbone as a pendant group i.e. extending away from the polymer backbone; this results in a side-chain LC polymer. These different types of polymer liquid crystal are represented schematically below. The mesogenic units are depicted by the rectangles. 
The side chain liquid crystal polymer can generally be thought of as containing a flexible polymer with rigid segments (the mesogenic unit) attached along its length by short flexible (or rigid) units as depicted in the schematic representation below. It is the anisotropic, rigid section of the mesogenic units that display orientational order in the liquid crystal phases. In order to affect the phases exhibited by the liquid crystal and the subsequent optical properties there are many features which can be altered, some of these features are particularly pertinent to side-chain liquid crystal polymers. One of these features is the flexible part that joins the mesogenic unit to the polymer backbone which is generally referred to as the spacer group. The length and flexibility of this spacer group can be altered. 
A number of side-chain liquid crystal polymers are known, for example see GB 2146787 A.
Liquid crystal polyacrylates are a known class of liquid crystal polymer (LCP). LCPs are known and used in electro-optic applications, for example in pyroelectric devices, non-linear optical devices and optical storage devices. For example see GB 2146787 and Makromol. Chem. (1985)186 2639-47.
Side-chain liquid crystal polyacrylates are described in Polymer Communications (1988), 24, 364-365 e.g. of formula: 
where (CH2)m is the flexible spacer group and X is the side-chain mesogenic unit and R is hydrogen or alkyl.
Side-chain liquid crystal polychloroacrylates are described in Makromol. Chem. Rapid Commun. (1984), 5, 393-398 e.g. of formula: 
where R is chlorine.
Patent Application PCT GB 94/00662 describes amongst other things the use of the Baylis-Hillman Reaction to make a range of novel liquid crystal polymers.
A method for the preparation of polyacrylate homo- or co-polymers having the following repeat unit is described in UK patent application GB 9203730.8
R1 and R2 are independently alkyl or hydrogen, R3 is alkyl, hydrogen or chlorine, m is O or an integer 1-20, W is a linkage group COO or OOC or O and X is amesogenic group.
One of the main problems with liquid crystal polymers is that they are extremely difficult to align in devices. Essentially there are two techniques which have been used for aligning liquid crystal polymers. It is possible to try to align the liquid crystal polymer in a similar manner as a low molar mass liquid crystal, which is described in more detail below. Alternatively, mechanical techniques can be used such as shearing. Typically mechanical shearing is performed over hot rollers, this technique is generally only suitable for flexible substrates. It is possible to shear a sample between glass slides however the glass slides cannot be sealed in the conventional manner.
Materials and Assembling Process of LCDs by Morozumi in Liquid Crystals Applications and uses, vol. 1 Ed. Bahadur, World Scientific Publishing Co, Pte. Ltd, 1990 pp 171-194 and references therein as the title suggests discusses methods for assembling liquid crystal devices.
The technique for aligning low molar mass liquid crystals is typically as follows. Transparent electrodes are fabricated on the surfaces of the substrates the substrates typically being made of glass e.g. glass slides. In twisted nematic or super twisted nematic devices, for example, an alignment process is necessary for both substrates. A thin alignment layer is deposited to align the liquid crystal molecules, typically either organic or inorganic aligning layers are used, for example SiO deposited by evaporation is a typical inorganic alignment layer. One method to form the alignment layer involves rubbing the surface by textures or cloths. Polyimides have also been employed for the surface alignment of layers. Polyimide is coated onto the substrates bearing electrodes by a spinner and then cured to form a layer of approximately 50 nm thickness. Then each layer surface is repeatedly rubbed in substantially one direction with an appropriate material. If the liquid crystal molecules are deposited on this layer they are automatically aligned in the direction made by the rubbing. It is often preferable if the molecules possess a small angle pre-tilt typically 2-3xc2x0. Higher pretilts are sometimes required.
The two substrates are then fixed together for example by adhesive and are kept separate by spacing materials. This results in uniform and accurate cell spacing. A typical adhesive is an epoxy resin. This sealing material is usually then precured. The electrodes may then be precisely aligned for example to form display pixels. The cell is then cured at, for example 100-150xc2x0 C. At this point the empty liquid crystal cell is complete.
It is at this point that the cell is filled with the liquid crystal material. The opening size in the sealing area of the liquid crystal cell is rather small therefore the cell can be evacuated, for example in a vacuum chamber, and the liquid crystal material forced into the cell via gas pressure. More than one hole in the sealing area may be used. The empty cell is put into a vacuum chamber and then the vacuum chamber is pumped down. After the cell has been evacuated the open region of the sealant is dipped into the liquid crystal material and the vacuum chamber is brought back to normal pressure. Liquid crystal material is drawn into the cell as a result of capillary action, external gases can be applied to increase the pressure. When the filling process is complete the hole or holes in the sealant is/are capped and the cell is cured at a temperature above the liquid crystal material clearing point to make the liquid crystal molecular alignment stable and harden the capping material.
Polymer liquid crystal molecules tend to be more viscous than low molecular weight liquid crystal materials and are therefore more difficult to align and more difficult to fill into devices. Only liquid crystal polymers with low molecular weights can be flow filled into a cell, and once a degree of polymerisation greater than around 30 or 40 repeat units is reached, most liquid crystal polymers become so viscous that flow filling cells is extremely difficult. Much slower cooling is needed in order to try and align liquid crystal polymers and this usually results in poor uniformity of alignment.
Poorly aligned liquid crystal molecules do not result in the fast switching high contrast materials and devices that are generally required.
The above techniques are suitable for many liquid crystal materials including those devices which use liquid crystal materials which exhibit and utilise the smectic mesophase e.g. ferroelectrics. Suitable alignment techniques may also be found in GB 2210469 B.
Devices containing ferroelectric liquid crystal mixtures can exhibit fast switching times (faster than 100 ms), Clark and Lagerwall, Appl. Phys. Lett., 36, 89,1980. They can bebistable which means that they can be multiplexed at high levels using a line-at-a-time scan technique. Ferroelectric materials continue to receive a large amount of investigative attention due to their application in high resolution flat panel displays. An important feature of devices containing liquid crystalline materials is that they should exhibit a fast response time. The response time is dependent on a number of factors, one of these being the spontaneous polarisation, denoted Ps (measured in nC cmxe2x88x922). By adding a chiral dopant to the liquid crystalline mixture the value of Ps can be increased, thus decreasing the response time of the device. Ferroelectric smectic liquid crystal materials, which can be produced by mixing an achiral host and a chiral dopant, use the ferroelectric properties of the tilted chiral smectic C, F, G, H, I, J, and K phases. The chiral smectic C phase is denoted SC* with the asterisk denoting chirality. The SC* phase is generally considered to be the most useful as it is the fastest switching. It is desirable that the material should exhibit a long pitchchiral nematic (denoted N*) and SA phase at temperatures above the chiral smectic phase in order to assist surface alignment in a device containing liquid crystalline material. Ferroelectric smectic liquid materials should ideally possess the following characteristics low viscosity controllable Ps and an SC phase that persists over a broad temperature range, which should include ambient temperature, and exhibits chemical and photochemical stability. Materials which possess these characteristics offer the prospect of very fast switching liquid crystal containing devices.
Jitao et al, Polymer vol.37, no 5, 1996, pp837-841 describe, interalia, the use of diallylamines for the synthesis of supernucleophilic reagents.
Ferroelectric LCDs by Dijon in Liquid Crystals Applications and Uses, vol. 1 Ed. Bahadur, World Scientific Publishing Co. Pte. Ltd, 1990 pp 350-360 and references therein discusses alignment processes for smectic phases for low molar mass materials. The filling of cells is believed to be possible only in the isotropic or nematic phase due to the viscosity of smectic phases. Generally materials with the following phase sequence give good alignment: 
whereas materials with the following phase sequences are more difficult to align: 
Typically, therefore, in order to use a liquid crystal material in the smectic phase it will involve heating the material to the nematic or isotropic phase and allowing it to cool slowly into an aligned smectic state. Should this technique be applied to a polymer liquid crystal material then the cooling time is usually very much longer in order to assist the alignment, though very often the alignment is poor.
There is a continued need for new liquid crystal polymers which possess the properties that allow them to be used in devices including one or more of the known electro-optic devices.
According to this invention there are provided materials of general formula I 
m=at least 5 and not greater than 50;
X3 is selected from formula IA: 
wherein Y is selected from CO or CH2;
n=1-15;
Q is independently selected from COO, OCO, O, S, CH2;
q=0-1 5 provided that when q=0 then only one of Q or Z is present;
Z is independently selected from O, S, single bond, COO, OCO, CH2, NH, NR, NR1 wherein R is C1-12 n-alkyl or C1-12 branched alkyl wherein the branched alkyl group may be achiral or chiral and R1 is (CH2)tE where t may be 1-15 and E can be selected from OH, CO2H, Br, Cl, I, SH, NH2, N(CH3)H; 
represents any mesogenic group;
X3 is also independently selected from H, OH, OCOR2, COOH, CO2R2, (CH2)pOH, (CH2)pCO2H, xe2x80x94(CH2)pOR2 or xe2x80x94(CH2)pCO2R2 and p=1-20, R2=H or C1-16 alkyl, when R2=C2-16 alkyl the terminal CH3 group may be replaced by Br or Cl;
provided that at least one of X3 is selected from formula IA.
The mesogenic group is further defined from general structure II 
A, B, D are selected from the following rings: 
the above rings may be substituted with one or more of the following substituents in at least one of the available substitution positions: F, Cl, Br, CH3, CN, OR, R and NCS where R is given by C1-5 branched or straight chain alkyl;
Z is selected from CN, F, Cl, NO2, R, OR, CO2R, CF3, OOCR, NCS, SCN, where R=straight chain or branched chain alkyl and may include from 1-16 carbon atoms and including where one or more non-adjacent CH2 groups may be substituted by CH(CN), CH(CF3), CH(Cl), CH(CH3) in chiral or non-chiral form; provided that the total number of rings present is not greater than 4;
W1, and W2 are independently selected from COO, OCO, single bond, CH2CH2, CH2O, OCH2, O, S, CHxe2x95x90CH, Cxe2x95x90C, OCO(CH2)x, COO(CH2)x, wherein x is 1-4.
Liquid crystal polymers described by the current invention may be any of the known types including homo or co polymers.
Y, in formula IA, may be CHOH and the OH groups used as a point of attachment for cross-linking agents to form elastomers.
According to a further aspect of this invention liquid crystal polymers of general formula I may be synthesised via the cyclization of a suitably functionalised diene.
According to a further aspect of this invention, liquid crystal polymers of formula I and variants thereof may be synthesised via the cyclisation of the following general formula III: 
According to a further aspect of the invention materials are provided of formula I wherein part of the repeating unit is made up from the following general formula IIIA: 
According to a further aspect of this invention compounds of Formula III are provided: 
wherein X3 is selected from formula IA
The invention will now be described with reference to the following diagrams by way of example only:
FIG. 1: is a general synthetic scheme for the production of polymers of general formula I
FIG. 2: is a general synthetic scheme for the production of polymers of general formula I when q=0
FIG. 3: is a general synthetic scheme for the production of polyamides
FIG. 4: is a general synthetic scheme for the production of polyamines
FIG. 5: illustrates a liquid crystal device
FIG. 6: illustrates a pyroelectric device
FIGS. 7 and 8 illustrate front and sectional views respectively of a reflective spatial light modulator drawn to different scales, in which the materials of the current invention may be incorporated.